Molecular Simulation of MoS2 Exfoliation.

A wide variety of two-dimensional layered materials are synthesized by liquid-phase exfoliation. Here we examine exfoliation of MoS2 into nanosheets in a mixture of water and isopropanol (IPA) containing cavitation bubbles. Using force fields optimized with experimental data on interfacial energies between MoS2 and the solvent, multimillion-atom molecular dynamics simulations are performed in conjunction with experiments to examine shock-induced collapse of cavitation bubbles and the resulting exfoliation of MoS2. The collapse of cavitation bubbles generates high-speed nanojets and shock waves in the solvent. Large shear stresses due to the nanojet impact on MoS2 surfaces initiate exfoliation, and shock waves reflected from MoS2 surfaces enhance exfoliation. Structural correlations in the solvent indicate that shock induces an ice VII like motif in the first solvation shell of water

Fluid dynamics: an emerging route for the scalable production of graphene in the last five years

Bulk applications of graphene in fields such as advanced composites, conductive ink, and energy storage require cheap and scalable graphene. Fortunately, in the last decade, liquid-phase exfoliation of graphite to give pristine graphene has been thought as a promising way to massive production of graphene at high efficiency and low cost, in terms of the cheap and abundant graphite source and a variety of cost-effective exfoliation techniques. Though many exfoliation techniques are available so far, this article will highlight the recent progress of fluid dynamics route which emerges as a promising scalable and efficient way for graphene production in the last five years. The emphasis is set on vortex fluidic devices and pressure- and mixer-driven fluid dynamics, with our perspectives on the latest progress, exfoliation mechanism, and some key issues that require further study in order to realize industrial applications.Comment: 18 figure

Mechanical Behavior Associated with Metallurgical Aspects of Friction Stir Welded Al-Li Alloy Exposed to Exfoliation Corrosion Test

Open Access articleThis research aims to investigate the effect of the exfoliation corrosion exposure time on the mechanical properties, the strength and elongation, of friction stir welded Al-Li alloy type 2195-T8. The exfoliation corrosion test was performed using the exfoliation corrosion (EXCO) solution, based on ASTM G34. The samples were exposed to different exposure times 24, 48, 96, 192 and 384 hours. The results showed that both the strength and elongation of the welded specimens - exposed to the exfoliation corrosion tests - were reduced. For example, the samples that were exposed to 384 hrs, their initial tensile strength and elongation were reduced by 13% and 17% respectively. The degradation process due to the exfoliation corrosion on the tensile strength was divided into three stages: fast (0-96 hrs: 443.7 MPa-416.3 MPa, the degraded rate was 0.29 MPa/h), steady (96-192 hrs: 416.3 MPa-413.4 MPa, the degraded rate was 0.03 MPa/h) and medium rate (192-384 hrs: 413.4 MPa-386.7 MPa, the degraded rate was 0.14 MPa/h). For the elongation, in general, the reduction was similar to the style of strength, but with different rates. The TEM images showed that this degradation was due to the dissolution of T1 (Al2CuLi) and S´ (Al2CuMg) phase. Also, the corrosion products and their role of adherence on the surface of the tested specimens were investigated. An empirical equation p-t (mechanical properties-exposure time) was established to calculate the effect of exposure corrosion time on the performance of welded specimens

Role of hydrogen in hydrogen-induced layer exfoliation of germanium

The role of hydrogen in the exfoliation of Ge is studied using cross-sectional transmission electron microscopy, atomic force microscopy, and multiple-internal transmission mode Fourier-transform infrared absorption spectroscopy and compared with the mechanism in silicon. A qualitative model for the physical and chemical action of hydrogen in the exfoliation of these materials is presented, in which H-implantation creates damage states that store hydrogen and create nucleation sites for the formation of micro-cracks. These micro-cracks are chemically stabilized by hydrogen passivation, and upon annealing serve as collection points for molecular hydrogen. Upon further heating, the molecular hydrogen trapped in these cracks exerts pressure on the internal surfaces causing the cracks to extend and coalesce. When this process occurs in the presence of a handle substrate that provides rigidity to the thin film, the coalescence of these cracks leads to cooperative thin film exfoliation. In addition to clarifying the mechanism of H-induced exfoliation of single-crystal thin Ge films, the vibrational study helps to identify the states of hydrogen in heavily damaged Ge. Such information has practical importance for the optimization of H-induced layer transfer as a technological tool for materials integration with these materials systems

Spectroscopic studies of the mechanism for hydrogen-induced exfoliation of InP

The motion and bonding configurations of hydrogen in InP are studied after proton implantation and subsequent annealing, using Fourier transform infrared (FTIR) spectroscopy. It is demonstrated that, as implanted, hydrogen is distributed predominantly in isolated pointlike configurations with a smaller concentration of extended defects with uncompensated dangling bonds. During annealing, the bonded hydrogen is released from point defects and is recaptured at the peak of the distribution by free internal surfaces in di-hydride configurations. At higher temperatures, immediately preceding exfoliation, rearrangement processes lead to the formation of hydrogen clusters and molecules. Reported results demonstrate that the exfoliation dynamics of hydrogen in InP and Si are markedly different, due to the higher mobility of hydrogen in InP and different implant-defect characteristics, leading to fundamental differences in the chemical mechanism for exfoliation

Solvent Exfoliation of Electronic-Grade, Two-Dimensional Black Phosphorus

Solution dispersions of two-dimensional (2D) black phosphorus (BP), often referred to as phosphorene, are achieved by solvent exfoliation. These pristine, electronic-grade BP dispersions are produced with anhydrous, organic solvents in a sealed tip ultrasonication system, which circumvents BP degradation that would otherwise occur via solvated oxygen or water. Among conventional solvents, n-methyl-pyrrolidone (NMP) is found to provide stable, highly concentrated (~0.4 mg/mL) BP dispersions. Atomic force microscopy, scanning electron microscopy, transmission electron microscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy show that the structure and chemistry of solvent-exfoliated BP nanosheets are comparable to mechanically exfoliated BP flakes. Additionally, residual NMP from the liquid-phase processing suppresses the rate of BP oxidation in ambient conditions. Solvent-exfoliated BP nanosheet field-effect transistors (FETs) exhibit ambipolar behavior with current on/off ratios and mobilities up to ~10000 and ~50 cm^2/(V*s), respectively. Overall, this study shows that stable, highly concentrated, electronic-grade 2D BP dispersions can be realized by scalable solvent exfoliation, thereby presenting opportunities for large-area, high-performance BP device applications.Comment: 6 figures, 31 pages, including supporting informatio

Computational investigation of the temperature influence on the cleavage of a graphite surface

Mechanical exfoliation of a graphite surface with an adhesive nanoasperity is studied under different temperatures ranging from 298 K to 2 K using classical molecular dynamics. Two types of the interlayer interaction are investigated. For a pairwise Lennard-Jones potential the complete removal of the upper graphene layer during the retraction of the nanoasperity occurs in the whole range of the temperatures considered. The results obtained using registry dependent potential, which takes into account electronic delocalization contribution besides the van der Waals one, exhibit more pronounced temperature dependence. In this case the exfoliation takes place for temperatures higher than 16 K, but beginning from 8 K down to 2 K the system behavior manifests qualitative changes with the absence of cleavage of the sample. Analytical estimates combined with the results of the simulations reveal that the contribution of the overlap of pi orbitals of carbon atoms plays an important role in the exfoliation of graphite.Comment: 24 pages, 16 figure

Deterministic Assembly of Arrays of Lithographically Defined WS2 and MoS2 Monolayer Features Directly from Multilayer Sources into Van der Waals Heterostructures

One of the major challenges in the van der Waals (vdW) integration of two-dimensional (2D) materials is achieving high-yield and high-throughput assembly of predefined sequences of monolayers into heterostructure arrays. Mechanical exfoliation has recently been studied as a promising technique to transfer monolayers from a multilayer source synthesized by other techniques, allowing the deposition of a wide variety of 2D materials without exposing the target substrate to harsh synthesis conditions. Although a variety of processes have been developed to exfoliate the 2D materials mechanically from the source and place them deterministically onto a target substrate, they can typically transfer only either a wafer-scale blanket or one small flake at a time with uncontrolled size and shape. Here, we present a method to assemble arrays of lithographically defined monolayer WS2 and MoS2 features from multilayer sources and directly transfer them in a deterministic manner onto target substrates. This exfoliate-align-release process - without the need of an intermediate carrier substrate - is enabled by combining a patterned, gold-mediated exfoliation technique with a new optically transparent, heat-releasable adhesive. WS2/MoS2 vdW heterostructure arrays produced by this method show the expected interlayer exciton between the monolayers. Light-emitting devices using WS2 monolayers were also demonstrated, proving the functionality of the fabricated materials. Our work demonstrates a significant step toward developing mechanical exfoliation as a scalable dry transfer technique for the manufacturing of functional, atomically thin materials